CN106009572A - PLA modified material applied to 3D printing of large casting molds, and method of PLA modified material - Google Patents
PLA modified material applied to 3D printing of large casting molds, and method of PLA modified material Download PDFInfo
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- CN106009572A CN106009572A CN201610563590.8A CN201610563590A CN106009572A CN 106009572 A CN106009572 A CN 106009572A CN 201610563590 A CN201610563590 A CN 201610563590A CN 106009572 A CN106009572 A CN 106009572A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention relates to the technical field of high polymer materials, the technical field of 3D printing, and the field of 3D casting, in particular to a PLA modified material applied to 3D printing of large casting molds, and a method of the PLA modified material. The invention provides the PLA modified material applied to 3D printing of large casting molds, and the PLA modified material comprises the following components: polylactic resin, an inorganic filler, a plasticizer, a flexibilizer, a coupling agent, a chain extender, an antioxidant, an anti-hydrolysis agent, a compatilizer, and a lubricant. To overcome defects in the prior art, the invention creatively develops the PLA modified material specially applied to 3D printing of large casting molds, and the PLA modified material has the advantages of being low in shrinking percentage, good in dimensional stability, high in strength, not liable to be affected with damp, low in price, easy to degrade, environment-friendly, non-toxic, non-irritant, non-pollution and the like.
Description
Technical field
The present invention relates to technical field of polymer materials, 3D printing technique field and 3D casting field, especially relate to a kind of for massive casting mould 3D print PLA is material modified and method.
Background technology
Polylactic acid (PLA) and copolymer thereof are a kind of synthesis macromolecular materials with excellent biocompatibility and biodegradable.It has nontoxic, nonirritant, plasticity machine-shaping strong, easy, is easily decomposed by the multiple-microorganism in nature or the enzyme in animal and plant body and replace, ultimately form water and carbon dioxide, free from environmental pollution, thus be considered as the most promising Biodegradable polymer material.Polylactic acid purposes is widely, biodegradable fiber, biodegradable plastics goods are used for it, and medicine slow-release material, osseous surgery material, operation suture thread, ophthalmic materials etc., new product and new application continue to bring out, and are defined as, by materialogy, the new material that new century is the most rising.
3D technology is most widely used 3D printing technique, 3D printing technique is applied in casting Technology Design, achieve the integration of design and analysis, manufacture process, substantially increase the efficiency of casting technique research and development, reduce Corporation R & D cost, improve casting quality.3D print die technology closely merges with conventional cast, is conducive to transformation and promotes the core competitiveness of conventional cast industry, and meanwhile, 3D printing technique is also brought into fast-developing passage by huge market capacity.
Compared with traditional fabrication casting mould, utilizing 3D printing technique to make casting mould, can make the casting mould of complexity, especially wooden model is difficult to the mould of molding.Realizing the one-body molded of complicated casting mould, improve Modeling precision, speed is fast, low cost, and Automated condtrol work, labor intensity is low, the recyclable recycling of surplus stock.Utilize 3D printing technique to make casting mould to have broad prospects.
But, because of polylactic acid poor toughness, to degrade uncontrollable, hydrophilic is poor, Shortcomings in the functional performance such as single, limits it and is more widely applied.Therefore, research worker has carried out substantial amounts of study on the modification on the basis of its structure and performance, thus extends the application of polylactic acid.But, the material modified 3D of being applied to of PLA sold in the market prints massive casting mould and there is also a lot of defect, such as moisture-sensitive, and printed material makes moist, smoothness impact extruded after melted, is easily caused shower nozzle blocking, is unfavorable for the molding of workpiece；During plastic material solidifies after melting, there is contractility, make in print procedure workpiece warpage or come off and printing complete after workpiece deformation, affect machining accuracy, waste printed material；When the most also can cause printing, bubble occurs.
Therefore, exploitation a kind of cheap, green low-carbon environment-friendly, good stability of the dimension, intensity high, have in the course of processing not plug-hole, not fracture of wire, without advantages such as buckling deformations, and the goods produced to have the PLA being exclusively used in 3D printing massive casting mould of preferable physical and mechanical properties and weatherability material modified.This has bigger realistic meaning for widening the application in Foundry Production of the 3D printing technique, and this is significant to the quality improving casting mould.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, creative develop that a kind of shrinkage factor is little, good stability of the dimension, intensity high, be difficult to make moist, and the 3D that is exclusively used in of cheap, degradable, environment-protecting asepsis, nonirritant, the advantage such as pollution-free to print the PLA of massive casting mould material modified.
In order to realize foregoing invention purpose, the present invention is accomplished in that
A kind of PLA printed for massive casting mould 3D is material modified, it is characterised in that include following components: polylactic resin, inorganic filler, plasticizer, toughener, coupling agent, chain extender, antioxidant, hydrolysis-resisting agent, compatilizer and lubricant.
Further, the quality proportioning of above component is respectively as follows: polylactic resin 100 parts, inorganic filler 10～30 parts, plasticizer 0.5～2 parts, toughener 0.1～0.5 part, coupling agent 1～5 parts, chain extender 0.5～1 part, antioxidant 0.1～1 part, hydrolysis-resisting agent 0.5～2 parts, compatilizer 1-5 part and lubricant 0.5-2 part.
Further, the kind of described polylactic resin is left-handed or dextrorotation or the mixture of the two, it is preferred that molecular weight 5～200,000, melt flow index 10～20g/10min.
Further, described inorganic filler is the mixture that a kind of or at least two in Pulvis Talci, calcium carbonate, montmorillonite, clay, calcium sulfate crystal whiskers, Muscovitum is formed, and its mesh number is 2500～5000 mesh.
Further, one or both compositions during described toughener is poly butylene succinate, succinic acid/mutual-phenenyl two acid bromide two alcohol ester, polycaprolactone, poly adipate succinic acid ester, polyethylene glycol succinate；Described plasticizer is at least one in dioctyl phthalate, tributyl 2-acetylcitrate, tricresyl phosphate, amber acid esters, triacetyl glycerine, dibutyl sebacate, adipic acid propanediol polyester or di-2-ethylhexyl maleate；Described coupling agent is one or more in KH-550, KH-560, KH-570, KH-580, KH-602, KH-791, KH-792, B201, N313；Described chain extender is 2-imidazolidinone.
Further, described antioxidant includes that two classes, a class are pentaerythritol tetrathioglycollate and triphosphite ester mixture, and both mass ratioes are 1:2, and another kind of is antioxidant 1010 and the compound composition of antioxidant 215, and both mass ratioes are 1:3～3:1.
Further, described hydrolysis-resisting agent is the mixture that a kind of or at least two in bisgallic acid acid anhydride, siloxanes, polycarbodiimide and single carbodiimide compound is formed, preferably polycarbodiimide and the mixture of single carbodiimides, wherein both mixing qualities ratio is for 1:9～9:1.
Further, described compatilizer be maleic anhydride grafting polymer, by methyl methacrylate, butadiene, the terpolymer of styrol copolymer copolymerization, GMA-ethylene-methyl acrylate terpolymer in one or more；Described lubricant is one or more in liquid paraffin, Tissuemat E, zinc stearate, ethylene bis stearamide.
Meanwhile, present invention provides a kind of preparation method material modified for PLA printed for massive casting mould 3D, it is characterised in that comprise the following steps:
A. raw material drying: by polylactic resin and toughener etc. at 80～100 DEG C, dry 4～6h, standby；
B. inorganic filler and coupling agent treatment: the aqueous solution that coupling agent is made into, then adding acetic acid adjusts pH value to 5, solution is joined in inorganic filler with the form of spraying, then mix with high-speed mixer, place half an hour, dry half an hour at 50～60 DEG C, then rise high-temperature 80～100 DEG C and inorganic filler is dried, standby；
C. it is blended: above-mentioned all material is proportionally added in mixed at high speed blender, stirs；
D. pelletize: being added in double screw extruder by the above-mentioned mixture stirred and carry out extruding pelletization, extrusion temperature 170～220 DEG C, screw speed is 40～100RPM, and rate of feeding is 5～15 RPM；
E. drying and packaging: above-mentioned particle is dried at 60 DEG C of vacuum 4h, then aluminium foil bag encapsulation, for 3D printer.
Beneficial effects of the present invention is as follows:
1. the present invention provides the PLA material modified degradable, environment-protecting asepsis, the nonirritant that print for massive casting mould 3D, pollution-free, and safety coefficient is high, improves and produces and the environment of use.
2. the PLA for massive casting mould 3D printing of present invention offer is material modified has superior mobility, rapid crystallization and high tenacity, and have and be difficult to make moist, the feature that shrinkage factor is low, viscosity is low, melt temperature is low, printing precision is high, combination property is high, is highly suitable for 3D and prints massive casting mould.
3. the present invention has carried out pretreatment in advance to inorganic filler and coupling agent, makes poly-lactic acid material mechanical performance significantly improve；The ruggedness of the mould that the poly-lactic acid material of the use present invention prints is considerably beyond conventional poly-lactic acid material, and can also bear bigger pressure and abrasion；Use the plasticizer of the present invention, i.e. add plasticity and the mobility of polymer, improve processability, make again goods have pliability；Use the coupling agent of the present invention, i.e. can compensate plastics and bring benefit owing to being dried problem that is bad or that the most thoroughly bring to the course of processing, it is possible to so that the rheological property of PLA and mechanical performance have reached desirable balance；Use the inorganic filler of the present invention, be possible not only to improve the rigidity of PLA, it is also possible to improve the toughness of PLA, meanwhile, polyesters toughener and inorganic filler also preferable work in coordination with activeness and quietness effect with having, and can realize toughness reinforcing increasing and carry out the most simultaneously.
4. it is short that the preparation method material modified for PLA for massive casting mould 3D printing that the present invention provides has technological process, the advantages such as equipment requirements is simple and convenient to operate, steady quality, production cost are low.
Detailed description of the invention
The present invention is directed to the deficiencies in the prior art, creative develop that a kind of shrinkage factor is little, good stability of the dimension, intensity high, be difficult to make moist, and the 3D that is exclusively used in of cheap, degradable, environment-protecting asepsis, nonirritant, the advantage such as pollution-free to print the PLA of massive casting mould material modified.
In order to realize foregoing invention purpose, the present invention is accomplished in that
A kind of PLA for massive casting mould 3D printing is material modified, and the quality proportioning of each component is: polylactic resin 100 parts, inorganic filler 10～30 parts, plasticizer 0.5～2 parts, toughener 0.1～0.5 part, coupling agent 1～5 parts, chain extender 0.5～1 part, antioxidant 0.1～1 part, hydrolysis-resisting agent 0.5～2 parts, compatilizer 1-5 part and lubricant 0.5-2 part.Wherein, the kind of described polylactic resin is left-handed or dextrorotation or the mixture of the two, it is preferred that molecular weight 5～200,000, melt flow index 10～20g/10min；Described inorganic filler is the mixture that a kind of or at least two in Pulvis Talci, calcium carbonate, montmorillonite, clay, calcium sulfate crystal whiskers, Muscovitum is formed, its mesh number is 2500～5000 mesh, this inorganic filler is possible not only to improve the rigidity of PLA, the toughness of PLA can also be improved, it is achieved toughness reinforcing increasing is carried out the most simultaneously simultaneously；Described toughener is one or both compositions in poly butylene succinate, succinic acid/mutual-phenenyl two acid bromide two alcohol ester, polycaprolactone, poly adipate succinic acid ester, polyethylene glycol succinate, meanwhile, polyesters toughener and inorganic filler preferable work in coordination with activeness and quietness effect with having；Described plasticizer is at least one in dioctyl phthalate, tributyl 2-acetylcitrate, tricresyl phosphate, amber acid esters, triacetyl glycerine, dibutyl sebacate, adipic acid propanediol polyester or di-2-ethylhexyl maleate, i.e. add plasticity and the mobility of polymer, improve processability, make again goods have pliability；Described coupling agent is one or more in KH-550, KH-560, KH-570, KH-580, KH-602, KH-791, KH-792, B201, N313；Described chain extender is 2-imidazolidinone, i.e. can compensate plastics and bring benefit owing to being dried problem that is bad or that the most thoroughly bring to the course of processing, it is possible to so that the rheological property of PLA and mechanical performance have reached desirable balance；Described antioxidant includes that two classes, a class are pentaerythritol tetrathioglycollate and triphosphite ester mixture, and both mass ratioes are 1:2, and another kind of is antioxidant 1010 and the compound composition of antioxidant 215, and both mass ratioes are 1:3～3:1；Described hydrolysis-resisting agent is the mixture that a kind of or at least two in bisgallic acid acid anhydride, siloxanes, polycarbodiimide and single carbodiimide compound is formed, preferably polycarbodiimide and the mixture of single carbodiimides, wherein both mixing qualities ratio is for 1:9～9:1；Described compatilizer be maleic anhydride grafting polymer, by methyl methacrylate, butadiene, the terpolymer of styrol copolymer copolymerization, GMA-ethylene-methyl acrylate terpolymer in one or more；Described lubricant is one or more in liquid paraffin, Tissuemat E, zinc stearate, ethylene bis stearamide.
Meanwhile, present invention provides a kind of preparation method material modified for PLA printed for massive casting mould 3D, comprise the following steps:
A. raw material drying: by polylactic resin and toughener etc. at 80～100 DEG C, dry 4～6h, standby；
B. inorganic filler and coupling agent treatment: the aqueous solution that coupling agent is made into, then adding acetic acid adjusts pH value to 5, solution is joined in inorganic filler with the form of spraying, then mix with high-speed mixer, place half an hour, dry half an hour at 50～60 DEG C, then rise high-temperature 80～100 DEG C and inorganic filler is dried, standby；
C. it is blended: above-mentioned all material is proportionally added in mixed at high speed blender, stirs；
D. pelletize: being added in double screw extruder by the above-mentioned mixture stirred and carry out extruding pelletization, extrusion temperature 170～220 DEG C, screw speed is 40～100 RPM, and rate of feeding is 5～15 RPM；
E. drying and packaging: above-mentioned particle is dried at 60 DEG C of vacuum 4h, then aluminium foil bag encapsulation, for 3D printer.
Embodiment one
The invention provides that a kind of shrinkage factor is little, good stability of the dimension, intensity high, be difficult to make moist, and the 3D that is exclusively used in of cheap, degradable, environment-protecting asepsis, nonirritant, the advantage such as pollution-free to print the PLA of massive casting mould material modified, the quality proportioning of each chemical constituent is: polylactic resin 100 parts；Pulvis Talci 10 parts, as inorganic filler；Dioctyl phthalate 1 part, as plasticizer；Poly butylene succinate 0.1 part, as toughener；KH-560 is 2 parts, as coupling agent；2-imidazolidinone is 0.5 part, as chain extender；Pentaerythritol tetrathioglycollate and triphosphite ester mixture are 0.3 part, and both mass ratioes are 1:2, as antioxidant；Polycarbodiimide and 0.7 part of the mixture of single carbodiimides, and both mass ratioes are 5:2, as hydrolysis-resisting agent；Maleic anhydride grafting polymer 2 parts, as compatilizer；Ethylene bis stearamide 0.5 part, as lubricant.
Meanwhile, present invention provides a kind of preparation method material modified for PLA printed for massive casting mould 3D, comprise the following steps:
A. raw material drying: by polylactic resin and toughener etc. at 80～100 DEG C, dry 4～6h, standby；
B. inorganic filler and coupling agent treatment: the aqueous solution that coupling agent is made into, then adding acetic acid adjusts pH value to 5, solution is joined in inorganic filler with the form of spraying, then mix with high-speed mixer, place half an hour, dry half an hour at 50～60 DEG C, then rise high-temperature 80～100 DEG C and inorganic filler is dried, standby；
C. it is blended: above-mentioned all material is proportionally added in mixed at high speed blender, stirs；
D. pelletize: being added in double screw extruder by the above-mentioned mixture stirred and carry out extruding pelletization, extrusion temperature 170～220 DEG C, screw speed is 40～100 RPM, and rate of feeding is 5～15 RPM；
E. drying and packaging: above-mentioned particle is dried at 60 DEG C of vacuum 4h, then aluminium foil bag encapsulation, for 3D printer.
Other embodiments are as shown in the table.
Last it is noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature is carried out equivalent.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (9)
1. the PLA printed for massive casting mould 3D is material modified, it is characterised in that include following components: polylactic resin, inorganic filler, plasticizer, toughener, coupling agent, chain extender, antioxidant, hydrolysis-resisting agent, compatilizer and lubricant.
2. the PLA for massive casting mould 3D printing as claimed in claim 1 is material modified, it is characterized in that, the quality proportioning of above component is respectively as follows: polylactic resin 100 parts, inorganic filler 10～30 parts, plasticizer 0.5～2 parts, toughener 0.1～0.5 part, coupling agent 1～5 parts, chain extender 0.5～1 part, antioxidant 0.1～1 part, hydrolysis-resisting agent 0.5～2 parts, compatilizer 1-5 part and lubricant 0.5-2 part.
3. the PLA for massive casting mould 3D printing as claimed in claim 1 is material modified, it is characterized in that, the kind of described polylactic resin is left-handed or dextrorotation or the mixture of the two, preferably, molecular weight 5～200,000, melt flow index 10～20g/10min.
4. the PLA for massive casting mould 3D printing as claimed in claim 1 is material modified, it is characterized in that, described inorganic filler is the mixture that a kind of or at least two in Pulvis Talci, calcium carbonate, montmorillonite, clay, calcium sulfate crystal whiskers, Muscovitum is formed, and its mesh number is 2500～5000 mesh.
5. the PLA for massive casting mould 3D printing as claimed in claim 1 is material modified, it is characterized in that, described toughener is one or both compositions in poly butylene succinate, succinic acid/mutual-phenenyl two acid bromide two alcohol ester, polycaprolactone, poly adipate succinic acid ester, polyethylene glycol succinate；Described plasticizer is at least one in dioctyl phthalate, tributyl 2-acetylcitrate, tricresyl phosphate, amber acid esters, triacetyl glycerine, dibutyl sebacate, adipic acid propanediol polyester or di-2-ethylhexyl maleate；Described coupling agent is one or more in KH-550, KH-560, KH-570, KH-580, KH-602, KH-791, KH-792, B201, N313；Described chain extender is 2-imidazolidinone.
6. the PLA for massive casting mould 3D printing as claimed in claim 1 is material modified, it is characterized in that, described antioxidant includes two classes, one class is pentaerythritol tetrathioglycollate and triphosphite ester mixture, and both mass ratioes are 1:2, another kind of is antioxidant 1010 and the compound composition of antioxidant 215, and both mass ratioes are 1:3～3:1.
7. the PLA for massive casting mould 3D printing as claimed in claim 1 is material modified, it is characterized in that, described hydrolysis-resisting agent is the mixture that a kind of or at least two in bisgallic acid acid anhydride, siloxanes, polycarbodiimide and single carbodiimide compound is formed, preferably polycarbodiimide and the mixture of single carbodiimides, wherein both mixing qualities ratio is for 1:9～9:1.
8. the PLA for massive casting mould 3D printing as claimed in claim 1 is material modified, it is characterized in that, described compatilizer be maleic anhydride grafting polymer, by methyl methacrylate, butadiene, the terpolymer of styrol copolymer copolymerization, GMA-ethylene-methyl acrylate terpolymer in one or more；Described lubricant is one or more in liquid paraffin, Tissuemat E, zinc stearate, ethylene bis stearamide.
9. the preparation method material modified for PLA printed for massive casting mould 3D, it is characterised in that comprise the following steps:
A. raw material drying: by polylactic resin and toughener at 80～100 DEG C, is dried 4～6h, standby；
B. inorganic filler and coupling agent treatment: the aqueous solution that coupling agent is made into, then adding acetic acid adjusts pH value to 5, solution is joined in inorganic filler with the form of spraying, then mix with high-speed mixer, place half an hour, dry half an hour at 50～60 DEG C, then rise high-temperature 80～100 DEG C and inorganic filler is dried, standby；
C. it is blended: above-mentioned all material is proportionally added in mixed at high speed blender, stirs；
D. pelletize: being added in double screw extruder by the above-mentioned mixture stirred and carry out extruding pelletization, extrusion temperature 170～220 DEG C, screw speed is 40～100 RPM, and rate of feeding is 5～15 RPM；
E. drying and packaging: above-mentioned particle is dried at 60 DEG C of vacuum 4h, then aluminium foil bag encapsulation, for 3D printer.
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